U.S. patent application number 09/813516 was filed with the patent office on 2003-01-30 for inkset for graphic art ink jet image printers.
Invention is credited to Kong lu, Kai, Ma, Zeying, Stramel, Rodney D., Yue, Shunqiong.
Application Number | 20030019395 09/813516 |
Document ID | / |
Family ID | 25212607 |
Filed Date | 2003-01-30 |
United States Patent
Application |
20030019395 |
Kind Code |
A1 |
Ma, Zeying ; et al. |
January 30, 2003 |
Inkset for graphic art ink jet image printers
Abstract
An ink jet inkset is provided for image printers, in particular
large format printers, for printing on both porous, non-porous, and
hybrid glossy media. The inket contains a black ink and one or more
color inks, said color ink composition comprises at least one
water-soluble dye and a vehicle comprising at least one co-solvent
and at least two different surfactants, a non-ionic surfactant and
a fluoro-surfactant. The total surfactant concentration ranges from
about 0.05 to 6 wt % of the ink composition. The non-ionic
surfactant is present in a range of about 0.05 to 3 wt % of the ink
composition, while the fluoro-surfactant is present in a range of
about 0.001 to 3 wt % of the ink composition. The ink formulation
that works well with porous, non-porous, and hybrid glossy media
and provides substantially instant ink drying and light fastness of
the ink. Further, the ink formulation evidences excellent image
quality. The ink can also pass harsh pen material compatibility
tests. The ink does not puddle on the surface of the orifice plate
in the default pen, yet has low viscosity. The ink is excellent in
pen reliability such as long decap time, no decel, no kogation, and
good drop directionality.
Inventors: |
Ma, Zeying; (San Diego,
CA) ; Kong lu, Kai; (San Diego, CA) ; Stramel,
Rodney D.; (San Diego, CA) ; Yue, Shunqiong;
(San Diego, CA) |
Correspondence
Address: |
HEWLETT-PACKARD COMPANY
Intellectual Property Administration
P.O. Box 272400
Fort Collins
CO
80527-2400
US
|
Family ID: |
25212607 |
Appl. No.: |
09/813516 |
Filed: |
March 21, 2001 |
Current U.S.
Class: |
106/31.59 ;
106/31.43; 106/31.58; 106/31.75; 106/31.86; 106/31.89 |
Current CPC
Class: |
C09D 11/40 20130101;
C09D 11/38 20130101 |
Class at
Publication: |
106/31.59 ;
106/31.89; 106/31.58; 106/31.86; 106/31.43; 106/31.75 |
International
Class: |
C09D 011/02 |
Claims
What is claimed is:
1. An ink-jet inkset for printing on porous, non-porous, and hybrid
glossy print media, said ink-jet inkset containing at least one
color ink and at least on black ink; the color ink comprising a
colorant, at least one water-miscible organic co-solvent, and at
least two surfactants, wherein one surfactant is a non-ionic
surfactant and one is a fluoro-surfactant; and wherein said black
ink is substantially free of fluoro-surfactants.
2. The ink-jet inkset of claim 1 wherein said color inks have a
surface tension of from about 14 to about 24 dyne/cm and said black
ink has a surface tension of from about 25 to about 43 dyne/cm.
3. The ink-jet inkset of claim 1 wherein said non-ionic surfactant
in said color ink has a concentration within a range of about 0.05
to 3 wt % of said ink and wherein said fluoro-surfactant has a
concentration within a range of about 0.001 to 3 wt % of said
ink.
4. The ink-jet inkset of claim 1 wherein said color ink comprises
three surfactants, wherein a first said surfactant is anionic, a
second said surfactant is non-ionic, and a third said surfactant is
either an anionic fluoro-surfactant or a non-ionic
fluoro-surfactant.
5. The ink-jet inkset of claim 3 wherein said first surfactant is a
diphenyl sulfonate derivative or a sulfonate, said second
surfactant is an acetylenic ethoxylated diol or a polyethylene
oxide ether or a polypropylene oxide ether, and said third
surfactant is selected from the group consisting of
(R.sub.FCH.sub.2CH.sub.2O).sub.xPO(O.sup.-NH.sub.4.su- p.+)y, where
x+y=3; (R.sub.FCH.sub.2CH.sub.2O).sub.xPO(O.sup.-NH.sub.4.sup-
.+).sub.y, where x+y=3 +hydrocarbon surfactant;
R.sub.FCH.sub.2CH.sub.2SO.- sub.3H,
R.sub.FCH.sub.2CH.sub.2SO.sub.3.sup.-NH.sub.4.sup.+;
C.sub.6F.sub.13CH.sub.2CH.sub.2SO.sub.3H,
C.sub.6F.sub.13CH.sub.2CH.sub.2- SO.sub.3.sup.-NH.sub.4.sup.+;
R.sub.FCH.sub.2CH.sub.2S--CH.sub.2CH.sub.2CO- O.sup.-Li.sup.+;
R.sub.FCH.sub.2CH.sub.2O(CH.sub.2CH.sub.2O).sub.xH;
R.sub.FCH.sub.2CH.sub.2O--(CH.sub.2CH.sub.2O).sub.yH; ammonium
perfluoroalkyl sulfonates;, potassium fluorinated alkyl
carboxylates;, fluorinated alkyl polyoxyethylene ethanols;
fluorinated alkyl alkoxylate; and fluorinated alkyl ethers.
6. The ink-jet inkset of claim 1 wherein said colorant in said inks
is a water-soluble dye.
7. The ink-jet inkset of claim 6 wherein said water-soluble dyes
comprises at least one dye selected from the group consisting of
black, yellow, cyan, and magenta dyes.
8. The ink-jet inkset of claim 7 wherein said yellow dye consists
essentially of Direct Yellow 132, wherein said cyan dye consists
essentially of Direct Blue 199, wherein said black dye consists
essentially of pacified reactive black 31, and wherein said magenta
dye is selected from the group consisting of Magenta 377 and a
mixture consisting essentially of Magenta 377 and Acid Red 52.
9. The ink-jet inkset of claim 1 wherein said at least one
water-miscible co-solvent is selected from the group consisting of
nitrogen-containing ketones; diols selected from the group
consisting of ethanediols, propanediols, butanediols, pentanediols,
hexanediols, heptanediols, and octanediols; C.sub.3-C.sub.6
alcohols and isomers thereof; glycol ethers selected from the group
consisting of polyalkylene glycols, and polymeric glycols;
thioglycol ethers; glycol ureas; and polyalkoxylated triols.
10. The ink-jet inkset of claim 9, wherein said at least one
water-miscible organic co-solvent is selected from the group
consisting of 2-pyrrolidone, N-methyl-pyrrolid-2-one (NMP),
1,3-dimethylimidazolid-2- -one, octyl-pyrrolidone, 1,2-ethanediol,
1,2-propanediol, 1,3-propanediol, 2-ethyl-2-hydroxymethyl-
1,3-propanediol, ethylhydroxy-propanediol, 1,2-butanediol,
1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol,
1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-heptanediol,
1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, propanol, butanol,
pentanol, and hexanol, diethylene glycol, triethylene glycol,
tetraethylene glycol, dipropylene glycol, tripropylene glycol,
tetrapropylene glycol, PEG 200, PEG 300, PEG 400, PPG 400, and
thiodiglycol.
11. The ink-jet inkset of claim 10 wherein said at least one
water-miscible organic co-solvent comprises a mixture of
2-pyrrolidone and 1,6-hexanediol.
12. The ink-jet inkset of claim 1 further comprising at least one
component independently selected from the group consisting of
buffers, biocides, and metal chelators.
13. An ink-jet inkset for printing on porous, non-porous, and
hybrid glossy print media, wherein said inkset contains an ink-jet
ink comprising (a) 0.5 to 5 wt % of at least one water-soluble dye
selected from the group consisting of yellow, cyan, and magenta
dyes and (b) a vehicle comprising 5 to 20 wt % of at least one
water-miscible organic co-solvent, about 0.05 to 6 wt % of a
surfactant mixture comprising an anionic surfactant, a non-ionic
surfactant, and an anionic fluoro-surfactant; 0 to about 5 wt % of
at least one component independently selected from the group
consisting of buffers, biocides, and metal chelators; and the
balance water; and wherein said inkset further comprises a black
ink having a surface tension greater than those of the color
inks.
14. The ink-jet inkset of claim 13 wherein said first surfactant is
a diphenyl sulfonate derivative or a sulfonate, said second
surfactant is an acetylenic ethoxylated diol or a polyethylene
oxide ether or a polypropylene oxide ether, and said third
surfactant is selected from the group consisting of
(R.sub.FCH.sub.2CH.sub.2O).sub.xPO(O.sup.-NH.sub.4.su- p.+)y, where
x+y=3; (R.sub.FCH.sub.2CH.sub.2O).sub.xPO(O.sup.-NH.sub.4.sup-
.+).sub.y, where x+y=3+hydrocarbon surfactant;
R.sub.FCH.sub.2CH.sub.2SO.s- ub.3H,
R.sub.FCH.sub.2CH.sub.2SO.sub.3.sup.-NH.sub.4.sup.+;
C.sub.6F.sub.13CH.sub.2CH.sub.2SO.sub.3H,
C.sub.6F.sub.13CH.sub.2CH.sub.2- SO.sub.3.sup.-NH.sub.4.sup.+;
R.sub.FCH.sub.2CH.sub.2SCH.sub.2CH.sub.2COO.- sup.-Li.sup.+;
R.sub.FCH.sub.2CH.sub.2O(CH.sub.2CH.sub.2O).sub.xH;
R.sub.FCH.sub.2CH.sub.2O--(CH.sub.2CH.sub.2O).sub.yH; ammonium
perfluoroalkyl sulfonates;, potassium fluorinated alkyl
carboxylates;, fluorinated alkyl polyoxyethylene ethanols;
fluorinated alkyl alkoxylate; and fluorinated alkyl ethers.
15. The ink-jet inkset of claim 13 wherein said yellow dye consists
essentially of Direct Yellow 132, wherein said cyan dye consists
essentially of Direct Blue 199, wherein said black dye consists
essentially of pacified reactive black 31, and wherein said magenta
dye comprises a mixture consisting essentially of Magenta 377 and
Acid Red 52.
16. The ink-jet inkset of claim 13 wherein said at least one
water-miscible co-solvent solvent is selected from the group
consisting of nitrogen-containing ketones; diols selected from the
group consisting of ethanediols, propanediols, butanediols,
pentanediols, hexanediols, heptanediols, and octanediols;
C.sub.3-C.sub.6 alcohols and isomers thereof; glycol ethers
selected from the group consisting of polyalkylene glycols, and
polymeric glycols; thioglycol ethers; glycol ureas; and
polyalkoxylated triols.
17. The ink-jet inkset of claim 16, wherein said at least one
water-miscible organic co-solvent is selected from the group
consisting of 2-pyrrolidone, N-methyl-pyrrolid-2-one (NMP),
1,3-dimethylimidazolid-2- -one, octyl-pyrrolidone, 1,2-ethanediol,
1,2-propanediol, 1,3-propanediol,
2-ethyl-2-hydroxymethyl-1,3-propanediol, eth-ylhydroxy-propanediol,
1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentane-diol,
1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol,
1,2-heptane-diol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol,
propanol, butanol, pentanol, and hexanol, diethylene glycol,
triethylene glycol, tetraethylene glycol, dipropylene glycol,
tripropylene glycol, tetrapropylene glycol, PEG 200, PEG 300, PEG
400, PPG 400, and thiodiglycol.
18. The ink-jet inkset of claim 17 where4in said at least one
water-miscible organic co-solvent comprises a mixture of
2-pyrrolidone and 1,6-hexanediol.
19. A method of printing an ink-jet ink on porous, non-porous, and
hybrid glossy print media, said method comprising: (a) providing an
ink-jet inkset, said ink-jet inkset comprising a black ink and a
color ink which, in turn, comprises at least one colorant, a
vehicle comprising at least one water-miscible organic co-solvent
and water, and at least two surfactants, wherein one surfactants is
a non-ionic surfactant and another surfactant is a
fluoro-surfactant; wherein said black ink has a higher surface
tension than those of said color inks; and (b) causing droplets of
said ink-jet ink compositions to be jetted through an orifice plate
onto said print media.
20. The method of claim 19 wherein said non-ionic surfactant has a
concentration within a range of about 0.05 to 3 wt % of said ink
and wherein said fluoro-surfactant has a concentration within a
range of about 0.001 to 3 wt % of said ink.
21. The method of claim 19 comprising three surfactants, wherein a
first said surfactant is anionic, a second said surfactant is
non-ionic, and a third said surfactant is either an anionic
fluoro-surfactant or a non-ionic fluoro-surfactant.
22. The method of claim 19 wherein said color inks have a surface
tension of from about 14 to about 24 dyne/cm and said black ink has
a surface tension of from about 25 to about 43 dyne/cm.
23. The method of claim 21 wherein said first surfactant is a
diphenyl sulfonate derivative or a sulfonate, said second
surfactant is an acetylenic ethoxylated diol or a polyethylene
oxide ether or a polypropylene oxide ether, and said third
surfactant is selected from the group consisting of
(R.sub.FCH.sub.2CH.sub.2O).sub.xPO(O.sup.31 NH.sub.4.sup.+).sub.y,
where x+y=3; (R.sub.FCH.sub.2CH.sub.2O).sub.xPO(O.-
sup.-NH.sub.4.sup.+).sub.y, where x+y=3+hydrocarbon surfactant;
R.sub.FCH.sub.2CH.sub.2SO.sub.3H,
R.sub.FCH.sub.2CH.sub.2SO.sub.3.sup.-NH- .sub.4.sup.+;
C.sub.6F.sub.13CH.sub.2CH.sub.2SO.sub.3H,
C.sub.6F.sub.13CH.sub.2CH.sub.2SO.sub.3.sup.-NH.sub.4.sup.+;
R.sub.FCH.sub.2CH.sub.2S--CH.sub.2CH.sub.2COO.sup.-Li.sup.+;
R.sub.FCH.sub.2CH.sub.2O--(CH.sub.2CH.sub.2O).sub.xH;
R.sub.FCH.sub.2CH.sub.2O--(CH.sub.2CH.sub.2O).sub.yH; ammonium
perfluoroalkyl sulfonates;, potassium fluorinated alkyl
carboxylates;, fluorinated alkyl polyoxyethylene ethanols;
fluorinated alkyl alkoxylate; and fluorinated alkyl ethers.
Description
TECHNICAL FIELD
[0001] The present invention is directed non-impact printers, more
particularly, to an inkset containing a black ink jet ink
composition for such printers. Specifically, this invention is
directed to large format image printers.
BACKGROUND ART
[0002] An image printer of high throughput requires, among other
things, fast-drying glossy media. By "image printer" is typically
meant graphic art, including photographic prints, printed on media
widths ranging from 4 to 60 inches. In some printers, the media
width may be varied, while in others, it may be fixed. Examples of
such image printers include Hewlett-Packard's DesignJet series
(2000, 2500CP, 2800, 3500CP, 3800, 5000, 5000PS); an example of a
glossy media printer includes Hewlett-Packard's Photosmart Printer.
The HP Deskjet 2K series can print on media widths of 35 inches,
the 3K series can print on media widths of 54 inches, and the 5K
series can print on media widths of 42 and 60 inches. The
aforementioned printers print on glossy media, among others.
[0003] While glossy media evidencing fast ink drying are required,
such media are porous and poor in lightfastness. To meet the broad
range of customer needs, a media of good lightfastness is also
necessary.
[0004] A number of inks have been previously disclosed and claimed;
see, e.g., U.S. Pat. No. 5,851,273, entitled "Dye Set for Improved
Ink-Jet Print Quality", issued on Dec. 22, 1998, to Peter C. Morris
et al; U.S. Pat. No. 5,788,754, entitled "Ink-Jet Inks for Improved
Image Quality", issued on Aug. 4, 1998, to Larrie A. Deardurff et
al; and U.S. Pat. No. 5,858,075, entitled "Dye-Set for Improved
Ink-Jet Image Quality", issued on Jan. 12, 1999, to Larrie A.
Deardurff et al, all assigned to the same assignee as the present
application. The inks of the first patent are employed in the
DesignJet printer, while the inks of the last two patents are
employed in the Photosmart Printer.
[0005] The inks disclosed and claimed in the foregoing patents
provide excellent image quality on non-porous glossy media such as
Hewlett-Packard's High Gloss Photopaper C6026A. However, these inks
do not perform as well with porous glossy media, nor on hybrid
glossy media (a combination of porous and non-porous), such as
Hewlett-Packard's Photopaper C6959. Hybrid glossy media exhibit
short dry times and good light fastness.
[0006] On the other hand, other Hewlett-Packard inks that are good
for porous glossy media do not print as well on the non-porous
glossy media.
[0007] Other issues constantly associated with the ink for imaging
are pen material compatibility and puddling. Because aggressive
surfactants are needed for better image quality, the ink often
causes delamination or detachment of pen components. Puddling on
the printhead surface is a big concern for ink jet printing.
Problems caused by puddling include drop mis-directionality,
massive ink accumulation on the nozzle (orifice) plate, pen service
difficulties, and increased ink contact/attack of pen
components.
[0008] Typically, ink flow channel design and firing chamber
architecture are designed to modulate puddling. Damped architecture
can control puddling by the reduction of ink refill speed. However,
that may add a negative effect on firing frequency response. In
addition, damped architecture could add more difficulties for pen
manufacturing.
[0009] Another approach is to increase the viscosity of ink. This
could be realized by adding a high molecular weight
surfactant/oligomer/polymer. Using viscous co-solvent or increasing
the total organic content can also raise ink viscosity. However,
image quality, defined by ink/media interaction, would not be
optimal.
[0010] Thus, an inkset is required that eliminates, or at least
minimizes, the foregoing problems, while providing improved image
quality print on porous, non-porous, and hybrid porous glossy
media, consistent with high throughput.
DISCLOSURE OF INVENTION
[0011] In accordance with the present invention, an ink jet inkset
is provided for image printers for printing on porous, non-porous,
and hybrid glossy media. The color ink compositions comprise at
least one water-soluble dye and a vehicle comprising at least one
co-solvent and at least two different surfactants, a non-ionic
surfactant and a fluoro-surfactant. The black ink can have an
alternative formulation without the presence of the
fluoro-surfactant.
[0012] The total surfactant concentration ranges from about 0.05 to
6 wt % of the ink composition. The non-ionic surfactant is present
in a range of about 0.05 to 3 wt % of the ink composition, while
the fluoro-surfactant is present in the color inks in a range of
about 0.001 to 3 wt % of the ink composition.
[0013] Because of differing needs in the ink formulations, it has
been found that an alternative ink composition with the black
colorant can be used along side the above mentioned color inks. So
while the color ink compositions should be formulated to decrease
puddling and help coalescence, the black ink composition can be
formulated without these limits. Additionally, the black ink are
formulated at a higher surface tension than the color inks; thus
providing for better reliability without the presence of
fluorosurfactants, like in the color inks.
[0014] The present invention provides an inkset that works well
with porous, non-porous, and hybrid glossy media. A printer, such
as the DesignJet 5000PS that accomodates the hybrid glossy media
will provide the customer with substantially fast ink drying while
maintaining the light fastness of the ink, compared to prior art
inks.
[0015] The inks of the present invention evidence excellent image
quality. The inks can also pass harsh pen material compatibility
tests. The inks do not puddle on the surface of the orifice plate
in the default pen, yet have low viscosity. The color inks have a
surface tension in the range of from about 14 to about 24 dyne/cm,
preferably from about 16 to about 23 dyne/cm. The black inks useful
herein have a surface tension in the range of from about 25 to
about 43 dyne/cm, preferably from about 27 to about 35 dyne/cm. The
differing surface tension of the inks allow for excellent pen
reliability such as long decap time (greater than 30 sec), no
decel, no kogation, and good drop directionality. The term "decap
time" refers to the time required for ink to crust in the nozzles
of the pen; a long decap time is desired. By "decel" is meant that
the velocity of ink drops decreases with time during continuous
firing of the pen, and is an undesirable property.
BEST MODES FOR CARRYING OUT THE INVENTION
[0016] The invention described herein is directed to improved inks
for printing inkjet images using commercially-available ink-jet
printers such as the DeskJet .RTM. family of printers, manufactured
by Hewlett-Packard Company, Palo Alto, Calif. The inks of the
present invention can produce true colors on a variety of glossy
media, whether porous, non-porous, or hybrid, with high throughput
and high lightfastness.
[0017] The inks of the present invention include black, yellow,
cyan, and magenta inks containing a black dye, yellow dye, a cyan
dye, and one or two magenta dyes, respectively. In particular, the
yellow dye is Direct Yellow 132, the cyan dye is Direct Blue 199,
and the magenta dye is Magenta 377 (Ilford AG, Switzerland), alone
or together with Acid Red 52. These dyes are all anionic dyes and
are associated with a sodium counterion.
[0018] The present yellow, cyan, and magenta aqueous ink
compositions each comprise in general from about 0.1 to 10 wt % of
the dye (or dyes) and a vehicle comprising the following components
(in wt % of the total ink composition): about 3 to 40 wt %,
preferably about 5 to 20 wt %, and most preferably about 13 to 15
wt % of at least one water-miscible organic co-solvent; about 0.05
to 6 wt % of a surfactant mixture comprising at least one non-ionic
surfactant and at least one fluoro-surfactant; 0 to about 5 wt % of
at least one component independently selected from the group
consisting of buffers, biocides, and metal chelators; and the
balance water. In an alternate embodiment, the surfactant mixture
comprises at least three surfactants: the non-ionic surfactant, an
anionic surfactant, and the fluoro-surfactant, which may be
non-ionic or anionic.
[0019] The present black aqueous ink composition comprises in
general from about 0.1 to 10 wt % of the dye (or dyes) and a
vehicle comprising the following components (in wt % of the total
ink composition): about 3 to 40 wt %, preferably about 5 to 20 wt
%, and most preferably about 13 to 15 wt % of at least one
water-miscible organic co-solvent; about 0.05 to 6 wt % of one or
more surfactants; 0 to about 5 wt % of at least one component
independently selected from the group consisting of buffers,
biocides, and metal chelators; and the balance water. The black
inks of this invention have a higher surface tension than those of
the color inks.
[0020] In the practice of the present invention, each ink color,
namely, cyan, yellow, and magenta, can comprise more than one dye
load. That is, there can be one or more ink-jet pens filled for
each ink color, each pen having a different dye load or a different
dye. For example, there can be two cyan pens, each one containing a
different dye load and/or a different cyan dye.
[0021] All concentrations herein are in weight percent of the total
ink composition, unless otherwise indicated. The purity of all
components is that employed in normal commercial practice for
ink-jet inks.
[0022] The yellow dye is Direct Yellow 132 (DY132), present in an
amount of about 1 to 5 wt %, preferably about 2.5 to 3.5 wt %. In
setting the concentration of the yellow dye, it is preferred that
the ink has an absorbance (A) of from about 0.0833 to about 0.1547
at the lambda maximum of 400 nm for a 1:10,000 dilution.
[0023] The cyan ink is Direct Blue 199 (DB 199), present in an
amount of about 0.1 to 5 wt %, preferably about 2.5 to 3.5 wt %. In
setting the concentration of the cyan dye, it is preferred that the
ink has an absorbance (A) of from about 0.07 to about 0.13 at the
lambda maximum of 620 nm for a 1:10,000 dilution.
[0024] The magenta ink is a mixture of Magenta 377 (M377) (Ilford
AG, Switzerland) and Acid Red 52 (AR52) and is present in a total
amount of about 0.1 to 5 wt %, preferably about 2.5 to 3.5 wt %. In
setting the concentration of the magenta dye, it is preferred that
the ink has an absorbance (A) of from about 0.0553 to about 0.1027
at the lambda maximum of 520 nm for a 1:10,000 dilution of the M337
dye and an absorbance (A) of 0.0266 to about 0.0494 at the lambda
maximum of 566 nm for a 1:10,000 dilution of the AR52 dye.
[0025] The black ink suitably employed in the practice of the
present invention can be dye-based or pigment-based. The black ink
can also be a composite of the three primary colors, yellow, cyan,
and magenta. Suitable dye-based black inks are disclosed and
claimed, for example, in U.S. Patent No. 4,963,189, entitled
"Waterfast Ink Formulations with a Novel Series of Anionic Dyes
Containing Two or More Carboxyl Groups", issued on Oct. 16, 1990,
to Suraj L. Hindagolla, and U.S. Pat. No. 5,725,641, entitled
"Lightfast Inks for Ink-Jet Printing", issued on Mar. 10, 1998, to
Cheryl A. MacLeod, both assigned to the same assignee as the
present application.
[0026] Suitable black pigment-based inks are disclosed and claimed,
for example, in U.S. Pat. No. 5,085,698, entitled "Aqueous
Pigmented Inks for Ink Jet Printers"; U.S. Pat. No. 5,221,334,
entitled "Aqueous Pigmented Inks for Ink Jet Printers"; and U.S.
Pat. No. 5,302,197, entitled "Ink Jet Inks", all assigned to E. I.
Du Pont de Nemours and Company. The preferred black dye is Pacified
Reactive Black 31. This ink, which is dye-based, has an absorbance
(A) of from about 0.084 to about 0.156 at the lambda maximum of 570
nm for a 1:10,000 dilution.
[0027] As indicated above, the inks of the present invention
comprise about 5 to 20 wt % water-miscible organic co-solvent. More
preferably, the inks comprise about 8 to 15 wt % organic
co-solvent.
[0028] The water-miscible organic co-solvents suitably employed in
the practice of the present invention include any of, or a mixture
of two or more of, such compounds as nitrogen-containing ketones,
such as 2-pyrrolidone, N-methyl-pyrrolid-2-one (NMP),
1,3-dimethylimidazolid-2-on- e, and octyl-pyrrolidone; diols such
as ethanediols (e.g., 1,2-ethanediol), propanediols (e.g.,
1,2-propanediol, 1,3-propanediol,
2-ethyl-2-hydroxymethyl-1,3-propanediol, ethylhydroxy-propanediol
(EHPD)), butane-diols (e.g., 1,2-butanediol, 1,3-butanediol,
1,4-butanediol), pentanediols (e.g. 1,2-pentanediol,
1,5-pentanediol), hexanediols (e.g., 1,2-hexanediol,
1,6-hexanediol, 2,5-hexanediol), heptanediols (e.g.,
1,2-heptanediol, 1,7-heptanediol), octanediols (e.g.,
1,2-octanediol, 1,8-octanediol); alcohols, such as C.sub.3-C.sub.6
alcohols (e.g., propanol, butanol, pentanol, and hexanol),
including isomers thereof (e.g., 1-propanol and 2-propanol); glycol
ethers and thioglycol ethers commonly employed in ink-jet inks,
such as polyalkylene glycols such as polyethylene glycols (e.g.,
diethylene glycol (DEG), triethylene glycol, tetraethylene glycol),
propylene glycols (e.g., dipropylene glycol, tripropylene glycol,
tetrapropylene glycol), polymeric glycols (e.g., PEG 200, PEG 300,
PEG 400, PPG 400), and thiodiglycol. Additional co-solvents include
hydantoins (glycol ureas) and derivatives thereof, such as a
hydantoin containing ethyl hydroxide and methyl groups, available
from Lonza, Inc. as Dantocol DHE, and polyalkoxylated triols, such
as Multranol 4012, which is a polyalkoxylated triol having a
molecular weight of about 440, available from Bayer.
[0029] Preferably, the organic co-solvent comprises a mixture of
2-pyrrolidone and 1,6-hexanediol.
[0030] Buffers optionally employed in the practice of this
invention to modulate pH can be organic-based biological buffers or
inorganic buffer, preferably organic-based. Examples of buffers
include tris(hydroxymethyl)aminomethane, available from companies
such as Aldrich Chemical (Milwaukee, Wis.),
4-morpholineethanesulfonic acid (MES), and
4-morphonlinepropanesulfonic acid (MOPS).
[0031] Metal chelators optionally employed in the practice of this
invention are used to bind transition metal cations that may be
present in the ink. Examples of preferably-employed metal chelators
include: EDTA, Diethylenetetraaminepentaacetic acid (DTPA),
trans-1,2-diaminocyclohexanetetraacetic acid (CDTA),
(ethylenedioxy) diethylene dinitrilotetraacetic acid (EGTA),
malonic acid, salicylic acid, or other chelators that can bind
transition metal cations.
[0032] Any of the biocides commonly employed in inkjet ink may
optionally be employed in the practice of this invention, such as
Nuosept 95, available from Huls America (Piscataway, N.J.); Proxel
GXL, available from Zeneca (Wilmington Del.); and glutaraldehyde,
available from Union Carbide Company (Bound Brook, N.J.) under the
trade designation Ucarcide 250.
[0033] The color inks of the present invention further comprise a
mixture of two or more surfactants, the total surfactant
concentration ranging from about 0.05 to 6 wt %. The surfactant
mixture comprises a non-ionic surfactant and a fluoro-surfactant.
Alternatively, the surfactant mixture comprises a non-ionic
surfactant, an anionic surfactant, and either a non-ionic or an
anionic fluoro-surfactant.
[0034] The concentration of the non-ionic surfactant is in the
range of about 0.5 to 3 wt % of the ink composition. One example of
a suitable non-ionic surfactant includes the SURFYNOL series, which
are acetylenic ethoxylated diols available from Air Products.
Another example of a suitable non-ionic surfactant includes the
TERGITOL series, which are polyethylene or polypropylene oxide
ethers available from Union Carbide.
[0035] The concentration of the optional anionic surfactant is in
the range of about 0.05 to 3 wt % of the ink composition. One
example of a suitable anionic surfactant includes the DOWFAX
series, which are diphenyl sulfonate derivatives available from Dow
Chemical. Another example of a suitable anionic surfactant is the
OT series, which are dioctyl sodium sulfosuccinates available from
Cytec Ind.
[0036] Examples of suitable fluoro-surfactants include the ZONYL
series, available from E. I. Du Pont de Nemours Company, and the
FLUORAD series, available from 3M Company. The ZONYL
fluoro-surfactants include
(R.sub.FCH.sub.2CH.sub.2O).sub.xPO(O.sup.-NH.sub.4.sup.+)y, where
x+y=3 and R.sub.F (FSP), FSP+hydrocarbon surfactant (FSJ),
R.sub.FCH.sub.2CH.sub.2SO.sub.3H,
R.sub.FCH.sub.2CH.sub.2SO.sub.3.sup.-NH- .sub.4.sup.+ (TBS),
C.sub.6F.sub.13CH.sub.2CH.sub.2SO.sub.3H,
C.sub.6F.sub.13CH.sub.2CH.sub.2SO.sub.3.sup.-NH.sub.4.sup.-
(FS-62), R.sub.FCH.sub.2CH.sub.2SCH.sub.2CH.sub.2COO.sup.-Li.sup.+
(FSA), R.sub.FCH.sub.2CH.sub.2O(CH.sub.2CH.sub.2O).sub.xH (FSO),
and R.sub.FCH.sub.2CH.sub.2O(CH.sub.2CH.sub.2O).sub.yH (FSN). The
moiety R.sub.F is F(CF.sub.2CF.sub.2).sub.z, where z=1-7 (FSP, FSJ,
FSO) or 1-9 (TBS, FSA). The FLUORAD fluoro-surfactants include
ammonium perfluoroalkyl sulfonates (FC-120), potassium fluorinated
alkyl carboxylates (FC-129), fluorinated alkyl polyoxyethylene
ethanols (FC-170C), fluorinated alkyl alkoxylate (FC-171), and
fluorinated alkyl ethers (FC-430, FC-431, FC-740).
[0037] Preferred fluoro-surfactants include ZONYL FSA, ZONYL FS-62,
and FLUORAD FC-129.
[0038] The concentration of the fluoro-surfactant ranges from about
0.001 to 3 wt %, preferably from about 0.01 to 1 wt %, and most
preferably from about 0.1 to 0.25 wt %. At a concentration less
than about 0.001 wt %, the benefits afforded by the presence of the
fluoro-surfactant are not realized, while a concentration greater
than about 3 wt % is not soluble in the ink.
[0039] The anionic and non-ionic surfactants, in combination with
the co-solvent(s), serve to reduce dry time and increase media
throughput and are compatible with the glossy media, whether
porous, non-porous, or hybrid. The fluoro-surfactant reduces
puddling of the ink-jet ink on the nozzle plate. As a result, the
pen orifice plate is cleaner. Better drop directionality and better
serviceability are obtained. Because of less ink build-up on the
print head, cross-contamination between colors is reduced.
[0040] As an example, an ink formulation containing 0.2 wt %
FLUORAD FS-62 can control puddling and allow the ink to have a low
viscosity (1.5 to 2.0 cps). Normally, for puddling benefit, an ink
viscosity of above 3.0 is preferred.
[0041] The low viscosity ink provides fast penetration rate on
glossy media. As a result, coalescence is minimized and image
quality is improved. The fast penetrating ink is more media
independent and works well for more than one glossy media. The
fluoro-surfactant also provides excellent bleed control.
[0042] Due to the effectiveness of the fluoro-surfactant on
puddling control, ink formulation freedom is expanded. Surfactants
or solvents that are poor in puddling performance can be
reconsidered and, indeed, can be used in combination with the
fluoro-surfactant.
EXAMPLES
Example 1
[0043] An example of an ink-jet ink composition in accordance with
the present invention is listed in Table I below. Table I lists the
compositions for the color inks, yellow, cyan, and magenta, and for
the color inks having reduced dye load, light cyan (20%) and light
magenta (20%). The black ink employed contained Pacified Reactive
Black 31, which has an absorbance (A) of 0.12 at 1:10,000
dilution.
1TABLE I Ink Formulation. Component/ Color Cyan Magenta Yellow
Light C Light M Metal 0.1 wt % 0.1 wt % 0.1 wt % 0.1 wt % 0.1 wt %
Chelator Biocide 0.15 wt % 0.15 wt % 0.15 wt % 0.15 wt % 0.15 wt %
FLUORAD 0.18 wt % 0.18 wt % 0.18 wt % 0.8 wt % 0.18 wt % FS-62
DOWFAX 0.32 wt % 0.32 wt % 0.32 wt % 0.32 wt % 0.32 wt % 2A1
SURFYNOL 0.16 wt % 0.16 wt % 0.16 wt % 0.l6 wt % 0.l6 wt % CT-111
Alkane Diol 9 wt % 9 wt % 9 wt % 9 wt % 9 wt % Nitrogen 4 wt % 4 wt
% 4 wt % 4 wt % 4 wt % Heterocyclic Ketone Na-DB199 A = 0.10 20% of
C @ 1/10K Na-M377 A = 0.079 20% of M @ 1/10K Na-AR52 A = 0.038 20%
of M @ 1/10K Na-DY132 A = 0.119 @ 1/10K DDI Water Balance Balance
Balance Balance Balance Total 100 wt % 100 wt % 100 wt % 100 wt %
100 wt %
[0044] DDI water is distilled deionized water.
[0045] pH adjusted with KOH for the vehicle to 7.2 to 7.3.
[0046] pH adjusted with KOH or HNO.sub.3 for final ink to 7.5 to
7.6.
[0047] Absorbance (A) spectra were measured on a Hewlett-Packard
8453 spectrophotometer at 1:10,000 dilution ("1/10K").
2TABLE I Black Ink Formulation. Component Black Metal Chelator 0.1
wt % Biocide 0.2 wt % Buffer 0.03 wt % DOWFAX 8390 0.5 wt %
SURFYNOL 0.4 wt % EHPD 4 wt % Nitrogen Heterocyclic 8 wt % Ketone
Na-PRB31 @1/10K A = 0.12 DDI Water Balance Total 100 wt %
[0048] DDI water is distilled deionized water.
[0049] pH adjusted with KOH for the vehicle to 7.2 to 7.3.
[0050] pH adjusted with KOH or HNO.sub.3 for final ink to 7.5 to
7.6.
[0051] Absorbance (A) spectra were measured on a Hewlett-Packard
8453 spectrophotometer at 1:10,000 dilution ("1/10K").
[0052] EHPD is ethylhydroxy-propanediol
[0053] The printed inks of Table I evidence no haze and have good
drytime and decreased puddling.
[0054] The dry time and smudge are measured and the results are
listed in Table II below. Smudge is measured by running a thumb
across the printed area at some time after printing to determine
whether or not the printed image was transferred or damaged.
3TABLE II Dry Time and Smudge Measurements. Present Invention Prior
Inks Dry Time Smudge Dry Time Smudge Porous instant no Hybrid <2
min no ca. 20 min. 2 hrs. non-porous <12 min no 20 min. no Note:
The "prior ink" is one substantially equivalent to that disclosed
and claimed in U.S. Pat. No. 5,851,273.
Example 2
[0055] An example of an ink-jet ink composition in accordance with
the present invention is listed in Table III below. Table III lists
the compositions for the color inks, yellow, cyan, and magenta, and
for the color inks having reduced dye load, light cyan (30%) and
light magenta (30%). The black ink employed contained Pacified
Reactive Black 31, which had an absorbance (A) of 0.12 at 1:10,000
dilution.
4TABLE III Ink Formulation. Component/ Cyan, Magenta, Yellow, Light
C, Light M, Color wt % wt % wt % wt % wt % Metal 0.1 0.1 0.1 0.1
0.1 Chelator Biocide 0.15 0.15 0.15 0.15 0.15 Buffer 0.05 0.05 0.05
0.05 0.05 ZONYL 0.8 0.8 0.8 0.8 0.8 FSA DOWFAX 0.32 0.32 0.32 0.32
0.32 2A1 SURFYNOL 0.16 0.16 0.16 0.16 0.16 CT-111 Alkane Diol 9 9 9
9 9 Nitrogen 4 4 4 4 4 Heterocyclic Ketone Na-DB199 A = 0.10 30% of
C @ 1/10K A = 0.03 Na-M377 A = 0.079 30% of M @ 1/10K A = 0.0237
Na-AR52 A = 0.038 30% of M @ 1/10K A = 0.0114 Na-DY132 A = 0.119 @
1/10K DDI Water Balance Balance Balance Balance Balance Total 100
wt % 100 wt % 100 wt % 100 wt % 100 wt %
[0056]
5TABLE III Ink Formulation. Component Black, wt % Metal Chelator
0.1 Biocide 0.2 Buffer 0.03 DOWFAX 0.5 SURFYNOL 0.4 EHPD 4 Nitrogen
Heterocyclic 8 Ketone Na-PRB31 @1/10K A = 0.12 DDI Water Balance
Total 100 wt %
[0057] DDI water is distilled deionized water.
[0058] pH adjusted with KOH for the vehicle to 7.1 to 7.2.
[0059] pH adjusted with KOH or HNO.sub.3 for final ink to 7.5.
[0060] Absorbance (A) spectra were measured on a Hewlett-Packard
8453 spectrophotometer at 1:10,000 dilution ("1/10K").
[0061] EHPD is ethylhydroxy-propanediol.
[0062] The inks of Table III evidenced the same dry time and smudge
results as in Table II above. The printed inks of Table III
evidence no haze and decreased puddling.
Examples 3
[0063] The following black inks were formulated as indicated:
6TABLE IV 3A 3C 3D Ink # % 3B % % Nitrogen 8 8 8 8 Heterocyclic
Ketone Fluoro Surfactant 0.2 -- -- -- Amphoric Surf. 1 -- -- --
Nonionic Surf. 0.5 0.25 0.25 0.4 Anionic Surf. 0.5 -- 1 0.5 EHPD --
8 8 4 1,6 Hexanediol 3 -- -- -- -- Buffer -- 0.15 0.15 0.15 Biocide
0.2 0.2 0.2 0.2 Metal Chelator -- 0.2 0.1 0.1 PRB31 0.15 0.15 0.15
0.15 PH 7.5 7.5 7.5 7.5 Surface tension 22.54 Around 30 around 30
around 30 (dynes/cm) Kogation 20% decrease No No No in drop wt
decrease decrease decrease Drop velocity Decrease No No No decrease
decrease decrease EHPD is ethylhydroxypropanediol PRB31-Pacified
Reactive Black 31 with Abs. @ 1/10k dilution.
[0064] Absorbance (A) spectra were measured on a Hewlett-Packard
8453 spectrophotometer at 1:10,000 dilution ("1/10K").
[0065] When the black ink is formulated to have a surface tension
of less than about 25 dynes/cm, as shown by 3A, there is a 20%
decrease in drop weight which reduces print quality and the drop
velocity is decreased which leads to misdirected drop
placement.
INDUSTRIAL APPLICABILITY
[0066] The inks of the present invention are expected to find use
in thermal ink-jet printers in combination with glossy print
media.
* * * * *